Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
  • C07C55/02—Dicarboxylic acids
  • C07C55/14—Adipic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
  • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds

Definitions

• the present invention relates to the preparation of adipic acid by hydrocarboxylation of pentenic acids, and, more especially, to the preparation of adipic acid by reacting water and carbon monoxide with at least one pentenic acid.
• European Patent Application No. 188,209 describes a process for the preparation of straight-chain dicarboxylic acids, in particular adipic acid, by reacting unsaturated monocarboxylic acids, notably pent-3-enoic acid, with carbon monoxide and water in the presence of a rhodium-based catalyst and an iodine-containing promoter, the reaction being carried out in a solvent such as methylene chloride at a temperature of 100° to 240° C. and under a total pressure of between 14 and 240 atm; a temperature ranging from 150° to 180° C. and a total pressure ranging from 24 to 40 atmospheres are considered to be preferred.
• a solvent such as methylene chloride
• a major object of the present invention is the provision of an improved process for the preparation of adipic acid by hydrocarboxylation of at least one pentenoic acid in the presence of rhodium or of a rhodium compound and of an iodine-containing promoter, wherein the reaction is also carried out in the presence of at least one cocatalyst selected from among iridium, ruthenium, osmium and compounds thereof.
• pentenic acid is intended pent-2-enoic acid, pent-3-enoic acid, pent-4-enoic acid and mixtures thereof.
• Pent-4-enoic acid provides good results, but is not readily commercially available.
• Pent-3-enoic acid whether used alone or in admixture with its isomers, is more particularly appropriate, taking account of its availability and the satisfactory results which it provides.
• the process according to the present invention requires the presence of a rhodium-based catalyst. Any source of rhodium values may be used.
• Exemplary sources of rhodium which are suitable for carrying out the process of the invention include:
• Rh metal Rh 2 O 3 ;
• RhCl 3 RhCl 3 .3H 2 O;
• RhBr 3 RhBr 3 .3H 2 O ;
• RhI 3 RhCl 3 .3H 2 O; Rh(acac) 3 ;
• Rh(Cod)(acac) 2 Rh 2 (CO 2 CH 3 ) 4 ; Rh 4 (CO) 12 ; and Rh 6 (CO) 16 .
• the amount of rhodium to be used may vary over wide limits.
• a catalytically effective amount expressed in moles of rhodium metal per liter of reaction mixture, ranging from 10 -3 to 10 -1 provides satisfactory results. Smaller amounts may be used; however, it is observed that the rate of reaction is low. Higher amounts present disadvantages only in respect of the economics of the process.
• the rhodium concentration ranges from 5.10 -3 to 10 -2 mol/l, inclusive.
• iodine-containing promoter are intended HI and the iodine-containing organic precursor compounds capable of generating HI under the conditions of the reaction, and in particular C 1 -C 10 alkyl iodides, with methyl iodide being more particularly preferred.
• RhI 3 may simultaneously constitute a useful source of rhodium as well as all or a fraction of the iodine-containing promoter.
• the amount of iodine-containing promoter to be used is typically such that the molar ratio I/Rh is greater than or equal to 0.1. It is not desirable for this ratio to be higher than 20. Preferably, the molar ratio I/Rh ranges from 1 to 4, inclusive.
• the presence of water is indispensable for carrying out the process according to the present invention.
• the amount of water to be used is such that the molar ratio of water/pentenic acid(s) ranges from 1 to 10, inclusive.
• a smaller amount presents the drawback of restricting the conversion.
• a larger amount is not desirable because of the loss in catalytic activity which is observed.
• the process according to the present invention also requires the presence of at least one cocatalyst selected from among iridium, ruthenium, osmium and compounds thereof.
• Ir metal IrO 2 ; Ir 2 O 3 ;
• Ru metal RuO 2 ; RuO 4 ;
• RuCl 3 RuCl 3 .3H 3 O ; RuBr 3 ; RuI 3 ;
• Os metal OsO; Os 2 O 3 ; OsO 2 : OsOF 4 ;
• the cocatalyst is advantageously selected from among iridium and the compounds thereof.
• the molar ratio of the cocatalyst, expressed as metal M with respect to rhodium, may vary over wide limits, for example from 0.05 to 50, inclusive.
• the M/Rh ratio preferably ranges from 0.1 to 5, inclusive.
• the process according to the present invention is advantageously carried out in the liquid phase.
• the reaction mixture may contain a solvent or diluent.
• solvents or diluents which are suitable according to the process of the invention: saturated aliphatic or aromatic carboxylic acids having up to 20 carbon atoms, and saturated aliphatic or aromatic hydrocarbons which are optionally chlorinated and are liquid under the conditions of reaction.
• a saturated C 1 -C 6 aliphatic carboxylic acid preferably acetic acid, is used.
• a chlorinated saturated aliphatic hydrocarbon is used, more preferably methylene chloride.
• the amount of solvent or diluent if such a solvent or diluent is indeed present in the reaction mixture, may be as high as 99% by volume of said mixture. To satisfactorily carry out the process of the invention, this amount will be greater than or equal to 10% and preferably range from 30% to 90% by volume, inclusive.
• the reaction temperature typically ranges from 100° to 240° C.
• this temperature will range from 160° to 190° C., inclusive.
• the reaction is carried out under a pressure higher than atmospheric pressure.
• the total pressure may vary over wide limits, for example from 2 to 150 bars. In general, good results are attained employing pressures ranging from 5 to 50 bars.
• Substantially pure carbon monoxide or technical grade carbon monoxide may be used.
• the adipic acid is separated off by any appropriate means, for example by extraction and/or crystallization.
• the autoclave was hermetically sealed, placed in an agitated furnace and connected to the compressed gas supply.
• reaction mass was analyzed by gas phase chromatography and by high performance liquid chromatography.
• Example 9 The procedure of Example 9 was repeated, but replacing IrCl 3 by the same amount of [IrCl(Cod)] 2 .
• Example 9 The procedure of Example 9 was repeated, but replacing IrCl 3 by the same amount of Ir 4 (CO) 12 .
• Example 9 The procedure of Example 9 was repeated, but replacing RhI 3 by an equivalent amount of [RhCl(Cod)] 2 and adding 0.3 mmol of HI to the batch.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Catalysts (AREA)

Applications Claiming Priority (2)

Publications (1)

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Citations (4)

• 1990
  • 1990-12-20 FR FR9016387A patent/FR2670779A1/fr active Granted
• 1991
  • 1991-12-16 ES ES91420452T patent/ES2054468T3/es not_active Expired - Lifetime
  • 1991-12-16 EP EP91420452A patent/EP0493273B1/fr not_active Expired - Lifetime
  • 1991-12-16 DE DE69102260T patent/DE69102260T2/de not_active Expired - Fee Related
  • 1991-12-18 CA CA002058043A patent/CA2058043C/fr not_active Expired - Fee Related
  • 1991-12-19 JP JP3337081A patent/JPH07113000B2/ja not_active Expired - Fee Related
  • 1991-12-20 KR KR1019910023658A patent/KR950011105B1/ko not_active IP Right Cessation
  • 1991-12-20 US US07/811,584 patent/US5268505A/en not_active Expired - Fee Related

Patent Citations (5)

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